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Rolf Huisgen's Classic Studies of Cyclic Triene Diels-Alder Reactions Elaborated by Modern Computational Analysis
- Source :
- Angewandte Chemie (International ed. in English). 59(30)
- Publication Year :
- 2020
-
Abstract
- Rolf Huisgen explored the Diels-Alder reactions of 1,3,5-cycloheptatriene (CHT) and cyclooctatetraene (COT) with the dienophiles maleic anhydride and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) to determine the kinetics and mechanisms of various electrocyclizations and Diels-Alder reactions. These reactions have been examined with density functional theory. Modern computational chemistry has provided information not previously available by experiment. Transition states for all the reactions have been identified, and their Gibbs energies are used to explain the experimental reactivities. Zwitterionic intermediates were not found in the [4+2] cycloadditions of both CHT or COT with PTAD and are thus not involved in these reactions. [2+2+2] cycloadditions, as an alternative path to the Diels-Alder products, are highly disfavored. Rapid double nitrogen inversion was found for the cycloaddition products with PTAD.
- Subjects :
- 010405 organic chemistry
Kinetics
Maleic anhydride
General Chemistry
General Medicine
010402 general chemistry
01 natural sciences
Catalysis
Transition state
Cycloaddition
0104 chemical sciences
chemistry.chemical_compound
Cyclooctatetraene
chemistry
Computational chemistry
Diels alder
Density functional theory
Nitrogen inversion
Subjects
Details
- ISSN :
- 15213773
- Volume :
- 59
- Issue :
- 30
- Database :
- OpenAIRE
- Journal :
- Angewandte Chemie (International ed. in English)
- Accession number :
- edsair.doi.dedup.....9db643f3a74cb1315252be0fbde92957